Substituted o-carbamylhydroxamate pesticides

ABSTRACT

SUBSTITUTED O-CARBAMLHYDROXAMATES SUCH AS METHYL O-(METHYLCARBAMYL)THIOLACETOHYDROXAMATE ARE USEFUL IN CONTROLLING A VARIETY OF PESTS.

United se 3,639,633 Patented Feb. 1, 1972 ice U.S. Cl. 424-327 23 Claims ABSTRACT OF THE DISCLOSURE Substituted O-carbamylhydroxamates such as methyl O-(methylcarbamyl)thiolacetohydroxamate are useful in controlling a variety of pests.

CROSS-REFERENCE TO RELATED APPLICATIONS This application is a divisional continuation-in-part of my copending application Ser. No. 670,494, filed Aug. 31, 1967, which in turn was a continuation-in-part of my then copending application Ser. No. 361,277, filed April 20, 1964, now abandoned, and my then copending application Ser. No. 602,134, filed Dec. 16, 1966, now abandoned.

BACKGROUND OF THE INVENTION This invention relates to carbamylhydroxamates and more particularly is directed to substituted O-carbamylhydroxamates and their use in controlling insects, other arthropod pests, and pestiferous mollusks.

Such pests as insects, ticks, mites, snails and slugs are a constant irritation and threat to man. They injure and destroy plants, consume stored food supplies, damage useful organic materials such as wood and wool, directly set upon man and animals and invade their dwellings contributing to the spread of some serious and harmful diseases. A major factor in the control of such pest organisms is the chemical pesticide. There is a continuing need for new chemical pesticides to replace those to which pest organisms have become resistant. There is also always a need for chemicals possessing greater activity or which are active against a broader variety of pests. And, of course, there is always a need for lower cost pesticides.

Various oximes and aldoximes are known in the art to possess biological activity. Such compounds as those of US. Pat. No. 3,063,823, for example, are disclosed to be herbicides, the compounds of US. Pat. No. 3,193,561 are disclosed to be effective insecticides, and the compounds of US. Pat. No. 3,217,037 are disclosed to be insecticides, miticides and nematocides. However, I have discovered a new class of carbamylhydroxamates which possess an exceptional combination of pesticidal properties.

SUMMARY OF THE INVENTION This invention concerns compounds of the formula ll R,-o=N-O-O-N wherein R is alkyl of 1 through 5 carbon atoms;

haloalkyl of 1 through 5 carbon atoms, containing 1 to 5 chlorine atoms, 1 to 5 bromine atoms or 1 to 11 fluorine atoms; alkoxyalkyl of 2 through 5 carbon atoms; carboalkoxyalkyl of 3 through 6 carbon atoms;

carboalkoxy of 2 through 6 carbon atoms; alkylthioalkyl of 2 through 5 carbon atoms; cycloalkyl of 3 through 5 carbon atoms; naphthyl; and

X z where X is hydrogen, fluorine, chlorine, bromine, nitro, cyano, trifluoromethyl and dimethylamino; Y is hydrogen, chlorine, alkyl of 1 through 4 carbon atoms, and alkoxy of 1 through 4 carbon atoms; and Z is hydrogen, or chlorine, with the limitation that Z is chlorine only when X and Y are chlorine; R is hydrogen or methyl; R is hydrogen or methyl; R is alkyl of 1 through 6 carbon atoms, benzyl and chlorobenzyl; and Q is oxygen or sulfur;

and the use of these compounds in controlling pests such as insects, ticks and mites.

The above compounds in addition to being efiective pest control agents demonstrate a good level of safety to seeds, fruit, foliage and other plant parts. They do not exhibit cumulative toxicity to mammals nor are they serious eye irritants. They are not readily absorbed through the skin by humans and animals. The latter facts, together with their good stability, facilitates safe handling and storage.

These compounds are readily metabolized or decomposed in soil, plants and animals to non-toxic, low molecular weight materials such as carbon dioxide. Thus, the compounds of this invention do not pose problems arising from long term build-up of toxic residual materials in the soil or in biological systems.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Preparation O-carbamylhydroxamates of Formula 1 are prepared by reacting a hydroxamate ester with sodium hydride in a suitable solvent such as tetrahydrofuran, adding the resulting sodium salt to a solution of phosgene, and then reacting the chloroformate intermediate with two equivalents of ammonia. The reaction is illustrated by the following equations:

wherein R R and Q have the same meaning as above.

O-carbamylhydroxamates of Formula 1 can also be prepared by reacting a hydroxamate ester with an alkali metal cyanate and trifluoroacetic acid in an inert solvent such as benzene. This reaction is illustrated by the following equation:

R R and Q are the same as above.

The hydroxamate ester intermediates required in the above synthesis can be prepared through reaction of an imino ether hydrochloride with hydroxylamine using conditions described in the literature. For example, see Ber., 29, 1149 (1896); Ber., 59, 2395 (1926); Ben, 69, 2352 (1936). A significantly improved method for carrying out this reaction is disclosed in copending application Ser. No. 571,963, now US. Pat. No. 3,374,260.

Thiolhydroxamate intermediates can also be prepared by chlorination of an aldoxime in an inert solvent to form the corresponding hydroxarnoyl chloride (see Ben, 27, 2197 (1894)), followed by reaction of the latter with the alkali metal salt of an alkyl mercaptan.

The O- (methylcarbamyl)hydroxamate of this invention are prepared by treating a hydroxamate ester, prepared as described above, with methyl isocyanate in the presence of an aprotic solvent such as benzene, toluene, methylene chloride, 1,2-dichloroethane, ethyl ether, tetrahydrofuran or their mixtures. Frequently it is advantageous to carry out the reaction in the presence of a small amount of 1,4-diazabicyclo[2.2.2]octane, triethylamine, or other basic material as a catalyst. This method is illustrated by the following equation:

R R and Q have the same meaning as above.

The O-(dimethylcarbamyl)hydroxamates of this invention can be prepared by reacting a hydroxamate ester with sodium hyrdride in a solvent such as tetrahydrofuran, and then treating the resulting sodium salt with dimethylcarbamyl chloride. This method is illustrated by the following equations:

R R and Q have the same meaning as above.

Pests controlled Insects, ticks and mites that are killed, repelled, prevented from reproducing or otherwise prevented from causing damage by the compositions of this invention are represented by, but not limited to, the following: Aphids- Apple aphid-Aphz's pomi Bean aphid-Aplzis fabae Cabbage aphidBrevicoryne brassicae Corn leaf aphid-Rh0pal0siphum maidis Corn root aphid-Anuraphis maidiradicis Cotton aphidAphis gossypii Greenbug-Schizaphis graminum Green peach, aphid-Myzus persicae 4 Aphids-Continued Potato aphidMacrosiphum euphorbiae Rose aphid-Macr0siphum rosae Woolly apple aphidEri0s0ma lanz'gerum Armyworms ArmywormPsuedaletia unipuncta Beet armyworm-Spodoptera exigua Fall armyworrn-Laphygma frugiperda Southern armyworn1-Pr0denia eridania Beetles Asiatic garden beetleMaladera castanea Bean leaf beetleMaladera castanea Blister beet1eEpicauta spp. Cigarette beetleLasi0derma serricorne Colorado potato bettle-Leplinotarsa decemlineata Japanese bettleP0pillz'a japonica Mexican bean beetleEpilachna varivestis Squash beetle- Epilachna borealz's Sugarcane beetleEuetheola rugiceps White-fringed beetleGraph0gnaihus leucoloma Boll weevil-Anthonomus grandis BollWorm-Heli0rhis Zea Borers European cornborer-0strinia nubilalis Peach tree borerSannin0idea exitz'osa Squash vine borer-Melittia cucurbitae Sugarcane borerDiatraea saccharalis Rice borers-Chilo spp. Butterflies Clouded su1fur.C0lias philodice Imported cabbageWorm-Pieris rapae Caterpillars-- Alfalfa caterpillar-Colias eurytheme Eastern tent caterpillarMalacos0ma americanum Forest tent caterpillar-Malacosoma disstria Corn earworm-Heli0this zea (see bollworm) Cotton leaf perforator--Bucculatrix thurberz'ella Cotton stainerDysdercus suturellus Flea beetles Corn flea beetle-Cheetoc'nema pulicaria Potato flea beetle-Epitrix cucumeris Tobacco flea beetle-Epitrix hirtipennis Fleahopper, cotton-Psalms seriatus Flies Hessian fly-Mayetiola destructor Horn fly-Haematobia irritans House fly-Musca domestica Stable fiy-Stomoxys calcz'trans Fruit flies- Mediterranian fruit fiy-Ceratitis capizata Mexican fruit fly-Anastrepha ludens Oriental fruit fiy-Dacus dorsalis German cockroach-Blattella germanica Grasshoppers-Melanoplus spp.

Camnula spp. Leaf rollers- Fruit tree leaf rollerArclzips argyrospilus Red-banded leaf roller-Argyrotaenia veiutilmlla Leafhoppers- Beet leaihopper-Circulifer terzellus Potato leafhopperEmp0asca fabae Sugarcane leafhopperPerkinsiella sacclzaricida Leafworrn, cotton-Alabanm argillucea Loopers Alfalfa loopen-Autographu californica Cabbage looperTrz'c/ 10plusia ni Maggot, seed-cornHylemya platura Mealybugs Citrus mealybug-Plamzococcus cit/i Pineapple mealybug-Dysmicoccus brevipes Mites- Citrus red mitePan0nychus citrz' Clover niite Bryobia praeiz'osa European red mite-Pmz01zychus ulnzz' Pacific spider mite-Tetranychus pacificus Two-spotted spider miteTetranychus urticae Mosquitoes- Common malaria mosquito-Anopheles quadrimaculatzrs Salt-marsh mosquito-Aedes sollicizans Southern house mosquitoCulex pipiens quinquefasciatus Moths Black army cutwormActebia femzica Black cutworm-Agrotis i psilon Codling mothCarp0capsa pomonella Diamondback mothPlutella maculipennis European Pine shoot mothRhyaci0nia buoliana Green cloverworm-Plathypena scabra Grape berry moth-Paral0besia viteana Gypsy moth-Portlzetria dispar Oriental fruit moth-Grapholitha molesta =Potato tuberwormPhth0rimeae operculella Spruce budwormCh0rist0neura fumiferana Tussock moth, white markedHemer0campa leucostigma Velvetbean caterpillarAnticarsia gemmatalis Pink bollworm--Pectin0ph0ra gossypiella Plum curculioC0n0lrachelus nenuphar Rootworms Northern corn r0otwormDiabr0tica longicornis Southern corn rootwormDiabr0tica undecz'mpunctata howardi Western corn r0otworn1Diabr0tica virgz'fera Slugs- Gray field slugDer0ceras laeve Gray garden slugDer0ceras reticulatum Spotted garden slug-Limax maximus Stink bugs Brown stink bug-Euschistus servus Green stink bug--Acr0sterm1m hilare Thrips- Onion thrips-Thrips tabaci Tobacco thrips-Franklz'niella fusca Tic-ks- American dog tick-Dermacentor variabilis Fowl tick-Argus persicus Tobacco budw0rm-Heli0this virescens Tobacco ho-rnworm-Manduca sexta Tomato hornworm-Manduca quinquemaculata Weevils-- Alfalfa weevilHypera postica Granary weevilSil0philus gralzarius Rice weevilSit0philus oryzae Sweetpotato weevilCylas formicarius elegantulus Whiteflies- Citrus black fiyAIeur0canthus woglumi Citrus White flyDialeur0des citri Preferred compounds Compounds of Formula 1 which are preferred because of their high order of pesticidal activity are those of the formula R is the same as in Formula 1; R is alkyl of 1 through 3 carbon atoms; and R is alkyl of 1 through 3 carbon atoms.

Particularly preferred compounds of 'Formula 1 because of their effectiveness against specific insects are:

Other particularly preferred compounds are:

Methyl O- (methylcarbamyl) p-nitrothiolbenzohydroxamate Methyl 0- methylcarbamyl)p-chlorothiolbenzohydroxamate Methyl O- (-methylcarbamyl)thiolisobutyrohydroxamate Methyl 0- (methylcarbamyl thiolpropionohydrox-amate Ethyl 0- (methylcarb amyl thiolacetohydroxamate tEthyl O-carbamylthiolacetohydroxamate Methyl O-carbamylthiolpropionohydroxamate Ethyl Ocarbamylthiolpropionohydroxamate Ethyl O- (methylcarbamyl thiolpropionohydroxamate Formulations Compositions of this invention suitable for practical use as pesticides will include one or more compounds of Formula 1 above either individually, as a complex, in admixture with each other, or in admixture with other pesticides and agricultural adjuvants such as resins, surfaceactive agents solid or liquid diluents and other materials as desired to produce wettable powders, suspensions, emulsifiable concentrates, dusts, solutions, granules, pellets or high-strength compositions.

The surface-active agents or surfactants, as they are sometimes called, useful in the formulations of this invention act as wetting, dispersing and emulsifying agents which assist dispersion of the active material in a spray. Additionally, the surfactants act as spreaders which aid in obtaining even coverage of the surfaces to be protected from insects and other pests. The surfactants can include such anionic, non-ionic and cationic agents as have been used heretofore in pesticidal compositions of similar type. A detailed list of such agents may be found in Detergents and Emulsifiers Annual (John W. McCutcheon, Inc.).

Anionic and non-ionic surfactants are preferred. Among the anionic surfactants, preferred ones are alkali and alkaline earth salts of alkylarylsulfonic acids, such as dodecylbenzenesulfonates and alkylnaphthalenesulfonates, dialkyl sodium sulfosuccinate esters, sodium lauryl sulfate, sodium N-methyl-N-oleoyltaurate, sodium dodecyldiphenyl ether disulfonate and the oleic acid ester of sodium isethionate. Among the non-ionic surfactants, preferred ones include octylphenyl polyethylene glycol ethers, dodecylphenyl polyethylene glycol ethers, polyoxyethylene derivatives of sorbitan fatty esters and long-chain alcohols and mercaptans, as well as polyoxyethylene esters of fatty acids.

Preferred dispersants are alkali and alkaline earth salts of lignosulfonic acids, salts of polymerized alkylarylsulfonates which are sold under the Daxad and Darvan trademarks, as well as methylcellulose, polyvinyl alcohol and the like.

Surfactants can be used in compositions of this invention in amounts of up to 50% by weight based on the total weight of the resulting insecticidal composition.

The compositions can contain, with or without a surfactant, one or more finely divided solid diluents such as natural silicates, e.g., talc, sepiolite, pyrophyllite; clays, e.g., montomorillonite, kaolinite, attapulgite, diatomaceous earth, synthetic magnesium silicate, synthetic fine silicas, calcium silicate, calcium sulfate, calcium carbonate, calcium phosphate, powdered charcoal and flours derived from natural sources such as walnut shell, redwood, cottonseed and the like. The finely divided solids can be used in the compositions of this invention at a concentration of 1 to 98% by weight based on the total weight of the resulting pesticidal composition. Preferred finely divided solid formulations are high-strength compositions and powders containing 1 to 25% of synthetic fine silica and 75 to 99% active ingredients; wettable powders containing 5 to 75% active ingredients, 0.5 to 50% surfactants, remainder finely divided solid diluents; dusts containing from 1 to 20% active ingredients; and dust concentrates containing 10 to active ingredients.

Organic liquids which are suitable for the preparation of solutions, suspensions and emulsifiable concentrates of the compounds of this invention include alcohols, glycols, Cellosolves, Carbitols, ketones, esters, sulfoxides, amides, parafiinic hydrocarbons, aromatic hydrocarbons, and halogenated hydrocarbons. Solvent combinations in which water miscible solvents are combined with water, are particularly useful. Ordinarily, solvent choice is dictated by the solubility of the active compound to be used and whether a suspension or solution is desired. With both polarand non-polar organic solvents, but particularly the latter, inclusion of 0.2 to 2.0 parts, per part of carbamate insecticide, of a phenolic compound containing at least one phenolic hydroxy group per molecule, functions to increase the solubility of some of the compounds of this invention such as methyl-O-(methylcarbamyl)thiolacetohydroxamate, ethyl O (methylcarbamyl)thiolacetohydroxamate, and methyl O-(dimethylcarbamyl)thiolacetohydroxamate. Such inclusion also improves the compatibility of these compounds with other insecticides such as EPN, methoxychlor or DDT, which are soluble in non-polar solvents solvents. Representative of such phenolic compounds are the cresols, o-t-butylphenol, a-naphthol, resorcinol and bis-phenol A.

Preferred solutions are those containing to 50% active ingredient and 50 to 80% solvent or solventphenolic compound combination. Preferred solvents are ethylene glycol methanol, methylene chloride dimethylformamide, Cellosolve, aqueous mixtures of these solvents, Xylene, heavy aromatic naphtha, isophorone and combinations of any of th se. Suspension formulations are generally preferred if the solubility of the active ingredient or active ingredients in the liquid carrier is less than about 0.1 percent.

For aerosol formulations low-boiling halogenated hydrocarbons are preferred as solvents and propellants, although they can be partially replaced by low-boiling hydrocarbons which act as propellants. Aerosol formulations ordinarily contain an organic or aqueous liquid in the range of 20 to 98% by weight based on the total weight of the pesticidal composition.

Formulations in the form of granules and pellets are physically stable, particulate compositions containing a compound of Formula (1) which adheres to or is distributed through a basic matrix of a coherent, inert carrier with macroscopic dimensions. In order to aid leaching of the active ingredient from the granule or pellet, a surfactant can be present.

Suitable carriers are preferably of mineral origin such as natural clays, some pyrophyllites, and vermiculite.

o 1 Other carriers can be of organic origin, such as granular corn cobs or charcoal. Suitable surfactants are anionic or non-ionic.

For the granule compositions of this invention, most suitable carriers are of two types. The first are porous, absorptive, preformed granules, such as preformed and screened granular attapulgite, granular corn cobs, granulated charcoal, or heat-expanded, granular, screened vermiculite. On such preformed granules, a solution of the active agent can be sprayed and will be absorbed at concentrations up to weight percent of the total weight. The active agent is preferably applied in a water solution when its solubility permits. In some instances, it is preferred to use hot rather than cold water to obtain a more concentrated spray solution. In other instances, an organic solvent or mixed organic-aqueous solvent is preferable to obtain increased solubility of the active ingredient. Ordinarily, if an organic solvent is used it is prcferably selected from among methylene chloride, methyl Cellosolve, dimethylformamide and the like.

Preformed granules can also be treated with a melt of active ingredient if the active ingredients melting point is sufficiently below its decomposition temperature. When this means of application is used, the active ingredient in a very finely divided form is deposited on the surface of 8 the granules such as by tumbling in a mixer. The finely divided active agent can if desired contain minor amounts of diluents such as synthetic silicas, natural clays and surfaceactive agents. After the active agent is distributed on the granules the granules are heated to above the melting point of the active agent preferably while tumbling is continued. The granules are then cooled and contain active ingredient within as well as fixed on their surfaces.

The second type of carrier suitable for granules as well as pellets is initially in a powder form. Powdered kaolin clays, hydrated attapulgite or bentonite clays such as sodium, calcium and magnesium bentonite, or powdered charcoal are blended with the active ingredient and the mixtures are then granulated or pelleted. Water-soluble salts can be included in the compositions to aid in disintegration of the granules and pellets in the presence of moisture. Such granules or pellets can be made containing 25 to 30 weight percent of active ingredient, but more frequently a concentration of 5 to 10 percent is preferred for optimum distribution. Such granular compositions are most useful in a size range of 15 to 60 mesh (U.S.S.), i.e., 0.25 to 1.4 millimeters.

The most preferred formulation for granules or pellets is 2 to 20 Weight percent active ingredient, 0 to 5 Weight percent surfactant and to 98 percent inert mineral carrier.

Sprayable granules can also be prepared. These are small solid particles containing 2 to percent active ingredient. The particles can be applied such as by suspending them in a liquid and spraying the suspension through a suitable nozzle.

Additional modifiers can be used to advantage in the compositions of this invention. Thus, although the compounds of Formula 1 are quite stable under most con ditions, the use of a desiccant, buffering agent or materials such as urea, which inactivate catalytic sites on diluent particles can prove desirable. Additives which will inhibit corrosion, reduce foam, reduce caking and increase fluocculation can also be used. In addition, bactericides, fungicides, bacteriostats and fungistats and other insecticides are often desirably present in the compositions of this invention in amounts of 0.025 to 10 parts by weight for each 1 part by weight of compound of Formula 1. Suitable biologically active compounds are mentioned below.

The compositions of this invention can be prepared by methods generally used for pesticidal compositions of similar type. The solid compositions, with the exception of granules and pellets are prepared in a blending operation where the active ingredients are either dry-blended with the diluents or impregnated by spraying a solution on a tumbling diluent mass. After blending the process will usually include passage through a grinder such as an attrition mill, a hammer mill or a fluid energy mill.

Solutions are prepared by stirring the combined ingredients; in some cases warming may speed solution and in others cooling or pressure may be required to prevent evaporation of the solvent. Aqueous and oil suspensions are prepared by mixing the insoluble active ingredient and other ingredients and ball-milling or sand-grinding the mixture to produce a concentrated slurry of very finely divided particles.

Combinations As mentioned above, in many instances, it is advantageous to combine the compounds of Formula 1 with each other and with other pesticides. Such combinations can be made by the user at the time of application or prepared by a manufacturer as a ready-to-use formulation in one of the manners described above.

Among the advantages of combinations are control of pests with a smaller total amount of chemical; control of pairs or communities of pests and pathogens; and regulation of the degree of residual effect. All of these advantages can be accomplished merely by selecting chemicuis for combination which complement one another in activity.

Ordinarily the chemicals combined will be used at from 0.1 to 3 times their normal use rate. However, rates are clearly dependent upon the specific chemicals combined, their intended use, and other obvious criteria.

Pesticides Which can advantageously be combined with the compounds of Formula 1 include, but are not limited to, the following:

1,2,3,4,10,10-hexachloro-1,4,4a,5,8,8a-hexahydro-1,4-

endoexo-S,8-dimethanonaphthalene (aldrin);

1,2,3,4,5,fi-hexachlorocyclohexane (lindane) 1,2,3,4,5, 6,7,8,8-octachloro-2,3,3a,4,7,7a-heXahydro-4,7-

methanoindene (chlordane);

1, 1,1-trichlro-2,2-bis(p-chlorophenyl) ethane (DDT) 1,2,3,4,10,10-hexachloro-6,7-epoxy-1,4,4a,5,6,7,8,8a-octahydro-1,4-endoexo-5,8-dimethanonaphthalene (dieldrin);

1,2,3,4,10,l0-hexachloro-6,7-epoxy-l,4,4a,5,6,7,8a,8a-

octahydro-l,4-endoendo-5,6-dimethanonaphthalene (endrin);

6,7,8,9,10,lO-hexachloro-l,5,5a,6,9,9a-hexahydro-6,9-

methano-2,4,3-benzodioxathiepin 3-oxide (Thi0dan);

1, (or 3a) ,4,5,6,7,8, 8-heptachloro-3a,4,7,7a-tetrahydr0- 4,7-methanoindene;

1,1,1-trichloro-2,2-bis(p-methoxyphenyl) ethane '(methoxychlor) 1, 1-dichloro-2,2-bis (p-chlorophenyl) ethane (TEDE) chlorinated camphene having a chlorine content of 67-69% (Toxaphene);

chlorinated terpenes having a chlorine content of ca.

66% (Strobane);

2-nitro-1,l-bis (p-chlorophenyl)butane;

l-naphthyl N-methylcarbamate (carbaryl);

methylcarbamic acid, ester with 4-(dimethylamino)-3,5-

dimethylphenol;

methylcarbamic acid, ester with 1,3-dithiolan-2-one oxime;

methyl N-methylthiolcarbamate;

methyl methylthiolcarba mate;

0,0-diethyl O- [2-isopropyl-4-methylpyrimid-6-yl] thiophosphate (diazinon);

0,0-dimethyl 1-hydroxy-2,2,2-trichloroethyl phosphonate;

0,0-dimethyl S-(1,2-dicarbethoxyethyl) dithiophosphate (Malathion);

0,0-dimethyl O-p-nitrophenyl thiophosphate (methyl parathion);

0,0-diethyl O-p-nitrophenyl thiophosphate (parathion);

0,0-dimethyl-O- 3-chloro-4-nitrophenyl) thiophosphate;

dl-2-cyclopentenyl-4-hydroxy-3-methyl-2- cyclopenten-l-one;

dl-chrysanthemumate;

0,0-dimethyl O-(2,2-dichlorovinyl) phosphate (DDVF mixture containing 53.3% Bulan, 26.7% Prolan and 20.0% related compounds;

0,0-dimethyl O-(2,4,5-trich1orophenyl) phosphorothioate;

0,0-dimethyl S- (4-oxo-1,2,3-benzotriazine-3 (4H) -ylmethyl) phosphorodithioate (Guthion);

bisdimethylamino phosphonous anhydride;

dimethyl phosphate of 3-hydroxy-N-methyl-ciscrotonamide (Azodrin);

0,0-diethyl O- (2-keto-4-methyl-7-u'-pyranyl) thiophosphate;

0,0-diethyl (S-ethylmercaptomethyl) dithiophosphate(phorate) calcium arsenate;

sodium aluminofluoride;

dibasic lead arsenate;

Z'-chloroethyl 1-methyl-2-(p-tert.-butylphenoxy)ethyl sulfite;

azobenzene;

ethyl 2-hydroxy-2,2 bis(4-chlorophenyl) acetate;

0,0-diethyl O-[2-(ethylmercapto) ethyl] thiophosphate;

2,4-dinitro-6-sec-butylphenol;

O-ethyl O-p-nitrophenyl 'benzenethiophosphate (EPN);

4-chlorophenyl 4-chlorobenzenesulfonate;

p-chlorophenyl phenyl sulfone;

tetraethyl pyrophosphate;

1,1-bis-(p-chlorophenyl) ethanol;

1, l-bis- (p-chlorophenyl) 2,2,2-trichloroethanol (Kelthane);

p-chlorophenyl p-chlorobenzyl sulfide;

bis- (p-chlorophenoxy) methane;

3-( l-methyl-2-pyrrolidyl) pyridine;

mixed esters of pyrethrolone and cinerolone keto-alcohols and two chrysanthemum acids;

cube and derris, both whole root and powdered;

ryanodine;

mixture of alkaloids known as veratrine;

dl-2-allyl-4-hydroxy-3-methyl-2-cyclopenten-l-one esterified with a mixture of cis and trans dl-chrysanthemum monocarboxylic acids;

butoxypolypropylene glycol;

p-dichlorobenzene;

2-butoxy-2-thiocyanodiethyl ether;

naphthalene;

1, l-dichloro-2,2-bis (p-ethylphenyl ethane;

p-dimethylaminobenzenediazo sodium sulfonate;

quinone oxyaminobenzooxohydrazone;

tetramethylthiuram monosulfide;

tetramethylthiuram disulfide (thiram);

metals salts of ethylenebisdithiocarbamic acid, e.g.,

manganese, zinc, iron and sodium salts;

pentachloronitrobenzene;

2,3-dihydro-S-carboxyanilido-6-methyl- 1,4-oxathiin;

n-dodecylguanidine acetate (dodine);

N-trichloromethylthiotetrahydrophthalirnide (captan);

phenylmercury acetate;

2,4-dichloro-6-(o-chloroanilino) -s-triazine (Dyrene) N-methylmercury-p-toluenesulfonanilide;

chlorophenolmercury hydroxides;

nitrophenolmercury hydroxides;

ethylmercnry acetate;

ethylmercnry 2,3-dihydroxypropylmercaptide;

'methylmercury acetate;

methylmercury 2,3-dihydroxypropylmercaptide (Ceresan L);

3,3'-ethylenebis(tetrahydro-4,6-dimethyl-2H-1,3,5-

thiadiazine-Z-thione) (Cylan);

methylmercury dicyandiamide;

N-ethylmercury p-toluenesulfonanilide;

l,4-dichloro-2,5-dirnethoxybenzene (chloroneb);

metal (e.g., iron, sodium and zinc), ammonium and amine salts of dialkyldithiocarbamic acids;

tetrachloronitronanisole;

hexachloro'benzene;

hexachlorophene;

methylmercury nitrile;

tetrachloroquinone;

N-trichloromethylthiophthalimide;

S-ethoxy-S-trichloromethyl-1,2,4-thiadiazole;

1,Z-dibromo-3-chloropropene;

dichloropropane-dichloropropene mixture;

ethylene di'bromide;

l-chloro-Z-nitropropane;

chloropicrin;

sodium dimethyldithiocar-barnate;

tetrachloroisophthalonitrile;

1- (n-butylcarbamoyl) -2-benzimidazolecarbamic acid methyl ester;

streptomycin;

2- 2,4,5 -trichlorophenoxy) propionic acid;

p-chlorophenoxyacetic acid;

1naphthaleneacetamide;

and

N-l-naphthylacetamide.

Of the above compounds, those which are insecticides and with which compounds of Formula 1 are preferably combined include DDT; TDE; EPN; Azodrin; Toxaphene; Strobane and Thiodan.

Fungicides and fungistats of the above list with which compounds of Formula 1 are preferably combined include PCNB; thiram; dodine; maneb; methylmercury 2,3 dihydroxypropylmercaptide; methylmercury acetate; N ethylmercury p toluenesulfonanilide; 1,4-dichloro- 2,5 dimethoxybenzene; 1 (n butylcarbamoyD-Zbenzimidazolecarbamic acid, methylester; N trichloromethylthiotetrahydrophthalimide; N trichloromethylthiophthalimide; sodium and calcium propionate; and 3,3-ethylenebis(tetrahydro 4,6 dimethyl) 2H 1,3,5 thiadiazine-Z-thione.

Bacteriostats and bacteriocides of the above list with which compounds of Formula 1 are preferably combined include tribasic copper sulfate and streptomycin sulfate.

Specific combinations which are preferred and their area of exceptional utility include:

(a) Methyl O (methylcarbamyl)thiolacetohydroxamate and methyl O-carbamylthiolacetohydroxamate in ratios ranging from 1:4 to 4:1 for use on cotton plants.

(b) Methyl O (methylcarbamyl)thiolacetohydroxamate and 1,4-dich1oro-2,S-dimethoxybenzene (chloroneb) in ratios ranging from 1:6 to 6:1 for use on cotton seed. The chloroneb can be replaced in this combination by one of the following compounds, their mixtures with each other or their mixtures with chloroneb: pentachloronitrobenzene, captan; tetramethylthiuram disulfide; 1-chloro-2- nitropropane; 5 ethoxy 3 trichloromethyl 1,2,4- thiadiazole; and p-dimethylaminobenzene-diazo sodium sulfonate. Such combinations are useful on seeds other than cotton including both vegetable and agronomic crops.

(c) Methyl O (methylcarbamyl)thiolacetohydroxamate, chloroneb, and 1-(n-butylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester, in ratios ranging from 1:4:4 to 4:1:1, for use on cotton seed and other crop seed.

(d) Methyl O carbamylthiolacetohydroxamate and DDT, in ratios ranging from 1:6 to 6:1 for use on cotton plants. In other combinations for this use, the DDT can be replaced by one of the following compounds, their mixtures with each other and their mixtures with DDT: endrin, carbaryl; Malathion, methyl parathion; parathion; Guthion and Toxaphene.

(e) Methyl O (methylcarbamyl)thiolacetohydroxamate and l-(n-butylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester, in ratios ranging from 1:3 to 3:1, for

use on rice plants in seed-bed, paddy or field for the control of insects and disease.

(f) Ethyl O carbamylthiolacetohydroxamate combined with EPN, carbaryl, Guthion, Malathion, methyl parathion or parathion in ratios ranging from 1:4 to 4: 1, for use on rice plants.

(g) Methyl O carbamylthiolacetohydroxamate combined with DDT, endrin, EPN, Toxaphene, Malathion, parathion, Guthion, carbaryl, or methoxychlor in ratios ranging from 1:5 to 5:1, for use on potato plants. The methyl O-carbamylthiolacetohydroxamate can be replaced in this combination by other compounds of Formula 1 such as methyl O-carbamylthiolpropionohydroxamate.

(h) Methyl O (methylcarbamyl)thiolacetohydroxa mate combined with parathion, aldrin, diazinon or phorate, in ratios ranging from 1:3 to 3:1 for application to soil prior to or during the plating of corn. The methyl 0 (methylcarbarnyl)thiolacetohydroxamate can be replaced in this combination by other compounds of Formula 1 such as ethyl O-(methylcarbamyl)thiolacetohydroxamate.

(i) Methyl O (methylcarbamyl)thiolacetohydroxamate combined with DDT, methoxychlor, Malathion, parathion, lead arsenate, Guthion, carbaryl or dieldrin in ratios ranging from 1:4 to 4:1, for use on apples and other crops.

(j) Methyl O carbamylthiolacetohydroxamate com bined with DDT, carbaryl, EPN, Toxaphene, methoxychlor or diazinon, in ratios ranging from 1:5 to 5:1 for use on corn plants.

(k) Methyl O cat'bamylthiolpropionohydroxamate combined with TDE, DDT, Guthion, Malathion, diazinon, parathion or carbaryl, in ratios ranging from 1:6 to 6: 1, for use on tobacco plants in seed-bed or field. The methyl 0 carbamylthiolpropionohydroxamate can be replaced in this combination by other compounds of Formula 1 such as methyl or ethyl O-(methylcarbamyl) thiolpropionohydroxamate.

(l) Ethyl O carbamylthiolacetohydroxamate and chlordane, in ratios ranging from 1:8 to 8:1, for use on surgarcane seed pieces in the furrow at the time of plantmg.

(m) Methyl O (methylcarbamyl)thiolacetohydroxamate combined with Toxaphene, carbaryl, endrin or Guthion, in ratios ranging from 1:12 to 12: 1, for use on sugarcane foliage.

(n) Methyl O carbamylthiolacetohydroxamate combined with methoxychlor, carbaryl, Malathion, DDT or Toxaphene, in ratios ranging from 1:4 to 4: 1, for use on shade trees or forest lands.

(0) Methyl O (methylcarbamyl)thiolacetohydroxamate combined with chlordane, DDT, diazinon or parathion, in ratios ranging from 1:5 to 5 :1, for use in soil prior to or during planting of potatoes.

(p) Methyl O (methylcarbamyl)thiolacetohydroxamate plus Guthion, diazinon, Malathion, parathion, methoxychlor, DDT, or Toxaphene, in ratios ranging from 1:5 to 5: 1, for use on cabbage or other cruciferous crops.

Complexes The compounds of Formula 1 form crystalline complexes with compounds such as urea, thiourea, and dicyandiamide, hereinafter referred to as complexing agents, in 1:1 molar ratios. Such complexes can be prepared readily by dissolving equal molar proportions of a compound of Formula 1 and a complexing agent in a mutual solvent such as methanol and then allowing the solvent to evaporate.

The complexes thus formed are ordinarily crystalline solids having sharp melting points. The solubility of the complex in many solvents will ordinarily differ from the parent compounds. These properties make the complexes particularly useful for isolating a compound of Formula 1 from its reaction mixture. They also make the complexes particularly suited for use in many formulations. Thus, for example, in the preparation of solutions, highstrength compositions and wettable powders complexes can be of particular advantage and in any of the compositions of this invention the complexes are ordinarily as suitable for use as, and should be regarded as the equivalent of, the compound of Formula 1.

Application In applying the compounds of this invention for pest control, the compound, of course, is applied in an amount sufiicient to exert the desired pesticidal action. The amounts required, however, to give pesticidal action are governed by such variables as temperature, time of the year, moisture, type of application, pests to be controlled, crop being treated and the like.

Compounds are applied to the locus or area to be pro tected. The application can be made directly upon the locus or area. to be protected from pests during the period of infestation. Alternatively, the application can be made in advance of an anticipated infestation so that the pests will ingest or contact the active compound and be killed.

More particularly the compounds of Formula 1 can be used to control insects and mites attacking living plants, by redistributing the compound over those plant surfaces already infested or subject to subsequent attack by these pests. Use rates for this type of application are in the range of 0.05 to 30 pounds of active ingredient per acre. More preferred rates are in the range of 0.1 to pounds per acre and the most preferred rates in the range of 0.2-7 lbs. per acre. Applications such as these may need to be repeated one or more times at intervals of 3 to days. Such applications are made with any of a variety of widely available types of equipment regularly used to apply pesticides to plants. In addition to conventional spray applications, the compounds of Formula 1 can be applied by ultra low volume application as concentrated solutions, used undiluted, at rates of from 1 pint to 2 gallons of total spray per acre. Conventional aerial sprays will ordinarily utilize diluted solutions at rates of from 2 to 20 gallons per acre. Mist blower sprays, utilizing diluted solutions, will ordinarily be made at rates of from 2 to 600 gallons per acre and preferably at rates of from 20 to 200 gallons per acre. To facilitate applications of this nature, the compounds of this invention can be formu- 'lated to improve handleabiilty or efiicacy as described previously.

Other effective methods of application include:

(a) Application to a part, such as the stem, of some plants, such as cotton, after which the chemical is systemically moved throughout the plant such that the entire plant is protected.

(b) Application to the seed of agricultural, horticultural and ornamental crops to protect the seed during storage and shipping prior to planting as well as to protect the seed and seedlings (as a result of systemic movement) from attack by insects and mites after planting. The preferred rates for application to seed are in the range of .01 to ounces of the active compound of this invention per 100 pounds of seed. The most preferred rates are in the range of l to 10 ounces per 100 pounds of seed.

(c) Application to soil in which plants are to be planted or are growing to protect seed and plants from attack by insects and mites. Such protection is against both soil insects attacking the roots and insects and mites attacking the above-ground parts of the plants. Preferred use rates are in the range of 0.1 to 50 pounds of active ingredient per acre of area actually treated. The most preferred rates are in the range of 0.25 to 20 pounds per acre. Such application includes placing the pesticidal composition in the furrow at the time of planting; mixing the composition into the soil at or after planting; and depositing the composition on the surface of the soil after planting so that it is carried down into the soil by rainfall or irrigation. Granular formulations are particularly useful in this type of application although other formulations can be used effectively.

((1) Application to the walls and floors of structures to control insects, ticks, and mites. Such applications to be repeated as needed. Preferred use rates for such applications are in the range of .001 to 2 pounds of active ingredients per 1,000 square feet of surface treated. The most preferred rates are in the range of .01 to 0.4 pound of active per 1,000 square feet of surface.

(e) Application to animals to control insects, ticks and mites causing injury or annoyance, or dissemination of disease. The compound of this invention to be applied to the animals to be protected by sprays, dusts or dips in such a way as to give a more or less uniform coating. Such applications to be repeated as needed.

(f) To land areas (including marsh or swamp) for the control of insects, ticks or mites causing injury or annoyance or disseminating disease to humans or animals. Preferred use rates are in the range of .01 to 9 pounds of active compound of this invention per acre 1 to 5 times a year. The most preferred rates are in the range of .03 to 3 pounds of active per acre on the same schedule.

(g) Application to leaves of plants to facilitate absorption and translocation within the treated leaves. Application will ordinarily be made at those rates first described above.

(h) Application to leaves of plants in such a manner so as to reduce absorption and translocation, and increase retention on external portions of the leaves. This increases the contact action of the compounds of Formula 1 and their residual activity by preventing absorption of the compounds into the plant and attendant deactivation of the compound by metabolism in the plant.

(i) Application in the form of baits to combat pests in areas where conventional spraying is not practical, such as household pests, pests living underground, and chewing pests attacking crop areas too large to be protected by spraying. These formulations are particularly useful for controlling pests in soybean, cotton and truck garden crops. Baits ordinarily will contain from 0.5 to 5 percent active ingredient and the food portion of the bait is selected according to the tastes of the pests being treated, Baits should be spread very thinly and uniformly to avoid danger to other forms of animal life.

(3') Application at low rates to insects as knockdown agents. Many insects, such as the spruce budWorm, when knocked out of foliage onto the ground, are unable to get back to the host plant to continue feeding. Application is made at rates of from 0.5 to 2 ounces per acre and thus reduces both the cost of treatment and the amount of chemical released into the biosphere.

In the applications enumerated above (a) through (f) the distribution of the compounds of this invention may be simplied and made more accurate through the use of the formulations and compositions described here- The following examples illustrate the invention. References to parts or percentages are by Weight unless otherwise specified. The compounds referred to in the examples as well as those referred to above and represented by Formulae 1 and 2 can exist as synand anti-isomers or as mixtures of these isomers.

EXAMPLE 1 To a slowly stirred mixture of 10.5 parts of methyl thiolacetohydroxamate, 50 parts of benzene and 13 parts of sodium cyanate, is added 15 parts of trifiuoroacetic acid. The temperature rises to 32 C. and is held there by external cooling, After addition of 50 parts of methylene chloride, the mixture is stirred for several hours, and then treated with 25 parts of water. A small amount of insoluble material is filtered off. The two phases of the filtrate are separated and the aqueous phase is reextracted with methylene chloride. Evaporation of the combined organic phases gives 5 parts of an oily solid which is recrystallized from isopropanol to yield 3.7 parts of methyl O-carbamylthiolacetohydroxamate.

The methyl 0 carbamylthiolacetohydroxamate is formulated and applied as follows:

Percent Methyl O-carbamylthiolacetohydroxamate 5.0 Sodium dioctyl sulfosuccinate 0.5 Polymerized alkylarylsulfonates ....4 1.0 Pyrophyllite 68.5 Attapulgite clay 25.0

EXAMPLE 2 Percent Methyl O-carbamylthiolacetohydroxamate 95.0 Synthetic silica r 5.0

The above high-strength composition is prepared by ElniMPLES coarse grinding and screening through a screen having 16 The following compounds are made in the manner of meshes/cm. methyl O-carbamylthiolacetohydroxamate of Example 1 This composition is added to water in an amount to by substituting an equivalent weight of the indicated provide 0.25 pound of the active ingredient per 100 5 starting material. The product is formulated and applied gallons. After the adequate time has passed to allow as in Example 1 to provide like results.

Starting material Product 5 Methyl acetohydroxamate Methyl O-carbarnylacetohydroxamate. 6 n-Butyl propionohydroxamate n-Butyl O-earbarnylpropionohydroxamate.

n-Butyl thiolpropionohydroxamate. n-Butyl O-carbamylthiolpropionohydroxamate. 8 Methyl thiolpropionohydroxamate.. \lethyl O-carbamylthiolpropionohydroxamate. 9 Ethyl thiolacetohydroxarnate Ethyl O-carbamylthiolacetohydroxarnate. 1O Methyl thiolisobutyrohydroxamate. Methyl O-carbarnylthiolisobutyrohydroxamate. 11 Benzyl thiolacetohydroxamate Benzyl O carbamylthiolaeetohydroxamate.

the active compound to go into solution, ordinarily be- EXAMPLE 12 tween 2 and minutes depending upon the temperature of water, the resulting solution is applied as a wetting spray to cabbage plants on which cabbage loopers (Tr'ichoplusia iii), are feeding. All of the cabbage loopers are killed by the spray.

DDT can be added to the above spray at the rate of 1.0 pound of active ingredient per 100 gallons. Such addition results in much improved control of harlequin bugs and stink bugs which often occur on cabbage along with cabbage loopers.

To a stirred suspension of 48 parts of 50% sodium hydride in mineral oil and 1170 parts of tetrahydrofuran is added in portions 201.5 parts of methyl p-chlorothiolbenzohydroxamate. The resulting sodium salt suspended in tetrahydrofuran is added in portions to 297 parts of phosgene in 1420 parts of ethyl ether maintained at 05 C. The excess phosgene is removed by distillation at reduced pressure. The resulting mixture is added in portions to 34 parts of ammonia dissolved in 1050 parts acetonitrile maintained at 0-10" C. After warming to ambient EYAMPLE 3 3O temperature the solids are filtered off and the filtrate is Percent extracted with hexane to remove mineral oil. The solvent Methyl O-carbamylthiolacetohydroxamate 25.0 is then removed yielding methyl O-carbamyl-p-chlorothiol- Dimethylformamide 25.0 benzohydroxarnate, which is recrystallized from ethanol- Methanol 50.0 water.

The above water-so1ub1e concentrate is prepared by 35 EXAMPLES 13'16 stirring the ingredients in a mixer. The concentrate is The following compounds are made in the manner of then added to water in an amount sufiicient to provide methyl O-(carbamyl)-p-chlorothiolbenzohydroxamate of 0.5 pound of the active ingredient per 100 gallons. White- Example 12 by substituting an equivalent weight of the marked tussock moths (Hemerocampa leucoszigma), indicated starting material.

feeding on blueberry plants are killed when the plants are sprayed at the rate of 100 gallons per acre with the water dilution.

Starting material Product 13-. \lethyl p-methylthlolbenzohydroxamate Methyl p-n1ethyl-O-carbamylthiolbenzohydrox- 14 Methyl o-n-butoxythiolbenzohydroxamate. lvlziili y l o-n-butoxy-O-carbamylthiolbenzohydroxarnate. 15 Methyl p-bromothiolbenzohydroxamate Methyl O-carbamyl-p-bromothiolbenzohydroxl6 Methyl p-chlorobenzohydroxamate lvli t l ii l b-carbamyl-p-chlorobenzohydroxamate.

EXAMPLE 4 EXAMPLE 17 Percent Methyl O-carbamylthiolacetohydroxamate 25.0 To surfed 8911mm composed of 201-5 Parts of Dimethylformamide 350 methyl p-chlorothlolbenzohydroxamate and 2 parts of 1,4- Methyl canosolva 40.0 diazabicyclo[2.2.2]octane in 1000 parts of benzene is added 65 parts of methyl isocyanate. After addition, the The above water so1ub1e concentrate i prepared by reaction mixture is heated at 40-50" C. for one hour. stirring the ingredients in a mixe Th concentrate i The solvent is removed under reduced pressure yielding then used to treat cotton seed at a rate of 6 ounces of methyl P-ChIOTO-O-(methylcarbamyl)thiolbefllohydroXathe active ingredient per 100 pounds of seed. Seed mate as a White Solid- The Product is Purified y 'y treated i hi Way grow to produce dli hi h kill tallization from a mixture of benzene and cyclohexane. cotton aphids (Aphis gossypii), which feed upon them The P yl P-C I IO-O-(methylcarbamyl)- up to 3 Weeks more ft r Planting Cotton thiolbenzohydroxamate, is formulated and applied as is improved if chloroneb is also applied to the cotton seed follows: along with the above concentrate at the rate of 6 ounces Percent of active per 100 pounds of seed. And cotton survival Mfithyl P- y y yis further improved if, as a third component of the dYOXamate treating preparation, Ceresan L is applied in an Dioctyl Sodium Sulfosllccinate amount to provide 3 ounces of Ceresan L per 100 Sodium ligfll'n Sulfonflte -0 pounds of cotton seed. The chloroneb in this mixture Methylaled 6611111056 L can be replaced by one or more of the following: penta- Fine Silica chloronitrobfanzene; p tetramethylthillram disulfide; The above components are blended and micropulverized m Q P P lf- P l/ to a particle size essentially less than 50 microns. The 4-th1adiazole; and p-drmethylarnmobenzenediazo sodium product can be used as a wettable powder or as a dust sulfonate. base.

17 A active dust is prepared by blending the ingredients below in an eflicient mixer such as a twin-shell blender prior to use:

1% Methyl p-fluoro-O-(methylcarbamyl)thiolbenzohydroamate can be formulated and used in like manner.

EXAMPLES 18-105 Percent Wettable powder described above 20.0 The following compounds are made in the manner of Pulverized talc 80-0 methyl p-chloro-O-(methylcarbamyl)thiolbenzohydroxa- The above dust formulation is applied to sweet corn by means of a tractor-powered duster at the rate of 10 to pounds of dust per acre. Infestations of the corn earworm (Heliothis zea), are effectively controlled by 10 this application.

mate of Example 17 by substituting an equivalent weight of the indicated starting material for the methyl p-chl0r0 thiolbenzohydroxamate of Example 17. The product is formulated and applied in like manner to provide like results.

Starting material Product 18 Methyl acetohydroxamate Methyl O-(methylcarbamyl)-acetohydroxamate. 19 Methyl n-butyrohydroxamate Methytl O-(metl1ylcarbamyl)-n-butyrohydrox ama e. 20 Ethyl acetohydroxamate Ethyl O-(methylcarbarnyl)-acetohydroxemate. 21 Methyl propionohydroxamate Methyl 0-(methylcarbamyl)-propionohydroxama e. 22 Methyl triehloroacetohydroxamate Mgthyl 0fimethylcarbamyl)-trlchloroacetohyroxama e. 23". Methyl n-hexanohydloxamate Methy l O-(methylcarbamyl)-n-hexanohydrox- 2-1113, 8. 24. n-Eexyl acetohydroxamate n-Hexyl O-(methylcarbamyl)-aeetohydroxerna e. 25 Methyl thiolpropionohydroxamate Mgthyl o-(tmethylcarbamyl)-thlolpropionohyroxama e. 26 Methyl thlolhexanohydroxamate Meithyl O-methylcarbamyl)-thiolhexanohyroxarna 9. 27 Methyl thiolacetohydroxamate Methyl 0-(methylcarbamyl)-thiolacetohydroxama e. 28 Methyl perfluorothiolhexanohydroxamate Methyl 0-(methylcarbamyl)-perlluorothlolhexanohydroxamate. 29 Methyl pentachlorothiolpropionohydroxamate Methyl O-(rnethylcarbamyl)-pentachlorothiolpropionohydroxamate. 30 Ethyl thiolacetohydroxamate Ethyl 0-(methylcarbamyl)-thiolecetohydrox- 31113 e. 81 Methyl thiolisobutyrohydroxamate Mgthyl 0-S:methy1carbamyD-thiolisobutyrohyroxarna 6. 32 Ethyl 2-methoxythiolacetohydroxamate Ethyl O-(methylcarbamyl)-2-methoxythlolacetohydroxamate. 33 n-Hexyl 3-methoxythiolpropionohydroxamate n-Hexyl 0-(methylcarbamyl)-3-methoxythiolproplonohydroxamate. 34 Methyl 3-is0propoxythiolpropionohydroxamate Methyl O-(methylcarbamyl)-3isopropoxythlolpropionohydroxamate. 35 Isopropyl tiolacetohydroxamate Is 3propyl Ct)-(methy10arbamyl)-thlolacetohyroxama e. 36 p-Chlorobenzyl tn'chlorothlolacetohydroxamate p-Chlorobenzyl O-(methylcarbamyl)trichlorothlolacetohydroxamate. 37 Methyl trichlorothiolacetohydroxarnate Methyl O-(methylcarbamyl)-triehlorothiolacetohydroxamate. 38 Methyl chloroacetohydroxamate Meithyl O-(gncthylcarbamyl)-chloroacetohyroxama e. 39 n-Butyl 3-chloropropionohydroxemate n-Butyl O-(methylcarbamyl)-3-chloroproplonohydroxamate. 4O Ethyl 3,4-diehlorobutyrohydroxamate Eth yl 0 (methy carbamyl)-3,4-dicl1lorobutyro y roxama 8. 41 Methyl 4,4,4-tribromobutyrohydroxamate Methyl O-(methyleaxbamyl)-4,4,4-trlbrom0- butyrohydroxamate. 42 11-Butyl2-flu0ropropionohydroxamate n-Butyl 0-(methylcerbamyl)-2-fiu0ropropionohydroxamate. 43 Methyl 3-methoxypropi0nohydroxamate Methyl 0-(methylcarbamyl)-3-methoxyproplonohydroxamate. 44 Methyl carbomethoxyacetohydroxamate Methyl O-(methylcarbamyl)-carbomethoxyacetohydroxamate. 45 Methyl cyclopentanecarbohydroxamate Methyl O-(methylcarbamyl)-cyelopentanecarbohydroxamate. 46 Ethyl 3-(methylthio)propionohydroxamate Ethyl O-(methylcarbamyl)-3-(methylthl0)- propionohydroxamate. 47 Methyl p-chlorobenzohydroxamate Methyl p-chloro-O-(methylcarbamyl)- benzohydroxamate. 48 Methyl p-bromobenzohydroxamate Methyl p-bromoO-(methylearbamyl)- benzohydroxamate. 49 Isopropyl thiolisohutyrohydroxamate Isopropyl O-(methylcerbamyl)-thiolisobutyrohydroxamate. 50 Methyl thlolpivalohydroxamate Methyl O-(methylcarbamyl)-thiolpivalohydroxamate. 51 Benzyl thiolaeetohydroxamate Benzyl O-(methylcarbamyl)-thlolacetohydroxamate. 52 p-Ohlorobenzyl thiolacetohydroxamate b-Chlorobeuzyl O-(methylcarbam DthiOI- acetohydroxamate. 53 Methyl chlorothiolaeetohydroxamate Methyl O-(methylcarbamyl)-chl0rothi0laeetohydroxamate. 54 n-Butyl 3-chlorothiolpropionohydroxamate. n-Butyl 0-(methylearbamyl)-3 chlerothlolpropionohydroxamate. 56 Ethyl 3,4-dichlorothiolbutyrohydroxamate. Ethyl O-(methylcarbamyl)-8,4-dichl0rothiolbutyrohydroxarnate 56 Methyl 4,4,4-tribromothiolbutyrohydroxamate. Methyl O-(methylearbamyl)-4,4,4-trlbromothiolbutyrohydroxamate. 57 Methyl 3-chlorothiolpropionohydroxamate Methyl O-(Inethylcarbamyl)-3-ehlorothiolpropionohydroxamate. 58 n-Butyl 2-fluorothiolpropionohydl'oxamaten-Butyl O-(methylcarbamyl)-2-fiuorothiolpropionohydroxamate. 59 Methyl perfluorothiolpropionohydroxamate Methyl O-(methylcarbamyl)-perfluorothiolpropionhydroxamate. 60 Methyl 2-(methylthio) thiolaeetohydroxamate Methyl O-(methylcarbamyl)-2-(methylthio)- thiolaeetohydroxamate. 61 Methyl 4-(Iuethylthio)thiolbutyrohydroxamate Methyl O-(methylcarbamyl)-4-(methylthio)- thiobutyrohydroxamate. 62 Methyl thiolcyclopropanecarbohydroxamate Methyl O-(methylcarbamyl)-thiolcyclopropanecarbohydroxamate. 63 Methyl thioleyelopentaneearbohydroxamate. Methyl O-(methylcarbamyl)-thiolcyelopentanecarbohydroxamate. 64 Methyl thiol-l-naphthohydroxamate Methyl O-(methylcarbamyl)-thlol-l-naphthohydroxamate.

TABLECntinue l Starting material Product Methyl thlol-Z-naphthohydroxamate Methyl O-(methylearbamyl)-thiol-2-naphthohydroxamate. 66 Methyl earboethoxythloliormohydroxamate. Methyl O(methylcarbamyl)-carboethoxythlol- Iormohydroxamate. 67 Methyl thlolbenzohydroxamate Methyl O-(methylcarbamyl)-thiolbenz0- hydroxamate. 68 N Ethyl thlolpropionohydroxamate Ethyl O-(methylcerbamyl)-thiolprop10no hydroxamate. 69 Propyl thlolhexanohydroxamate Propyl O-(methylcarbamyl)-thiolhexanohydroxamate. 70 Ethyl m-ehlorothiolbenzohydroxarnate Ethyl m-ehloro-O{methylearbamybthiolbenzohydroxamate. 71 Methyl p-hromothiolbenzohydroxamate... Methyl p-bromo-O-(methylearbamyl) thiolbenzohydroxamate. 72 Methyl p-(triiluoremethyl)thlolbenzo- Methyl p-(trifiuoromethyl)-O-(methylcarban1yl) hydroxamate. thiolbenzohydroxamate. 73 n-Butyl psee-butylthiolbenzohydroxamate n-Butyl p-secbutyl-O-(methylcarbamyl) thiolbenzohydroxarnate. 74 Methyl earbomethoxythlolacetohydroxamate. Methyl O-(rnethylcarbamyl)-earbomethoxythiolacetohydroxamate. 75 Methyl p-methoxythiolbenzohydroxamate. Methyl O-(methylearbarnyl)-p-methoxythiolbenzohydroxamate. 76 Methyl o-fluorothiolbenzohydroxamete Methyl O-(methylcarbamyl)-o-fluorothiolbenzohydroxamate. 77 n-Propyl-omethoxythiolbenzohydroxamate n-Propyl o-methoxy-O-(methylcarbamyl)- thiolbenzohydroxamate. 7s Methyl p-et y o nzohydroxemate Methyl O(methylcarbamyD-p-ethylthlolbenzohydroxamate. 79 Methyl p-dimethylamin0thiolbenzo- Methyl O-(methylcarhamyl)-p-dimethyl hydroxarnate. aminotliiolbenzoliydroxamate. 80 Methyl m-nitrothiolbenzohydroxarnate Methyl O-(methylcarbamyl)-m-nitr0thiolbenzohydroxarnate. 81 Methyl p-cyanothiolbenzohydroxamate Methyl O-(methylcarbamyD-pcyanothrolbenzohydroxamate. I 82 Methyl p-nitrothiolbenzohydroxamate Methyl O-(methylcarbamyl)-p-nltrothiolhydroxamate. 83 Methyl 2-bromo-4chlorothiolbenzo- Methyl O-(rnethylcarbamyl)-2-bromo-4-chlo ohydroxamate. thlolbenzohydroxamate. 84 Methyl 3,4-dicl1lorothiolbenzohydroxamete Methyl O-(rnethylearbamyl)-3,4diehloroth1olbenzohydroxamate. S5.-. Methyl 2,4,5-trichlorothiolbenzohydroxamate Methyl O(methylcarbamyl)-2,4,5-trichlorothiolbenzohydroxamate. 86. v. Methyl 3,4,5-trichlorothiolbenzohydroxamate. Methyl O-(methylcarbamyl)-3,4,5-trichlorothiolbenzohydroxemate. 37 Methyl 5-ehloro-2-methoxythiolbenzo- Methyl O-(methylcarbamyl)-5-chl0ro-2-methoxhydroxamate. ythiolbenzohydroxamate. 88 Methyl 2-chl0ro-4-cyanothiolbenmhydroxamatm Methyl O-(methylcarbamyl)-2-chloro-4-cyanothiolbenzohydroxamate. 89 Methyl 4-bromo-Z-methylthiolbenzo- Methyl O-(methylcarbamyl)-4-br0mo-2- hydroxamate. inethylthiolbenzohydroxamate. 90 Methyl 2-chloro4-nitrothiolbenzohydroxamate Methyl O-(rnethylcarbamyl)-2-chloro-4- 1iitrothiolbenzohydroxamate. 91 Methyl 3-chl0ro-4-dimethylamiuothiol- Methyl O-(rnethylcarbamyD-B-chloro-4-dibenzohydroxamate. methylaminothiolbenzohydroxamate. 92 Methyl 2-chl0ro-4-(trifluoromethyl)thiol- Methyl O-(methylcarbamyl)-2-chloro-4- benzohydroxamate. trifluoromethylthiolbenzohydroxamate. 93 Methyl 3-bromothiolpropionohydroxamate Methyl O-(methylearbamyl)-3-br0m0thiolpropionohydroxamate. 94 Methyl carbobutoxythiolacetohydroxamute Methyl O-(methylcarbamyl)carb0butoxythlolacetohydroxamate. 95 Methyl 3-earbomethoxythiolpropiono- Methyl O-(methylcarbarnyl)-3-carbomethoxhydroxamate. ythiolpropionohydroxamate. 96 Methyl carbopentoxythiolformohydroxamate.. Methyl O-(methylearbamyl)-carbopentoxyth1olforrnohydroxamate. 97 n-Hexyl thiolacetohydroxarnate n-Ial'exyl O-(methylcarbamyl)-thiolacet0hyroxamate. 98 Methyl 3-(methylthlo)-thi0lpr0piono- Methyl O(methylcarbamyl)-3-(methylthio)- hydroxamate. thiolpropionohydroxamate. 99 Propyl thlol t-methylvalerohydroxamate Propyl O-(methylcarbamyl)-thiol-4-methylvalerohydroxamate. 100 .l Methyl methoxythiolacetehydroxamate Methyl O-(methylcarbamyl)-rnethoxythlolacetohydroxamatei 101 Methyl o-methylthiolbenzohydroxamate Methyl O-(methylcerbamyl)-o-methylthiolbenzohydroxamate. 102 Methyl 4-tert.-butylthl0lbenzohydroxamate Methyl O-(methylearbamyl)-4tert.-butylthlolbenzohyclroxamate. benzohydroxamate. 103 Methyl 3-brorno-4-sec.-bntylthiolbenzo- Methyl O-(methylearbzmyl)-3-bromo-i-sec.-

hydroxamate. hntylthiolbenzohydroxamate. 104 Methyl 2-n-butoxy-3-nitrothiolbenzo- Methyl O-(methylearbamyl)-2-n-butoxy-3- hydroxamate. nitrothiolbenzohydroxamte. 105 Methyl 2-methoxythlolbenzohydroxamate Methyl O(rnethylcarbamyl)-2 methoxythiol benzohydroxamate.

EXAMPLE 106 To a stirred suspension of 48 parts of 50% sodium hydride with mineral oil in 730 parts of tetrahydrofuran is added over a one-hour period 89 parts of methyl thiol- 65 acetohydroxamate. The temperature is maintained at 20 sodlum hgnosulfonate Methyl O- (dimethylcarbamyl) thiolacetohydroxamate Sodium a1kylnaphthalenesulfonate 30 C. After gas evolution subsides, 107.5 parts of di- T; methylcarbamyl chloride is added over a one-hour period apu g1 with the temperature kept between 15 and 25 C. Stirring The ingredients are blended, coarsely ground through is continued for one hour at room temperature and the 70 a hammer mill and then passed through a fluid energy mill solids are removed by filtration. The solvent is removed to produce particles substantially all below 10 microns. under reduced pressure yielding methyl O-(dimethylcar- The 1101156 y (Musca domestica) is controlled in barns bamyl)thiolacetohydroxamate. by using 1 pound of the above formula in 2.5 gallons of The product, methyl O(dimethylcarbamyl)thiolacetowater and spraying the walls, floors, cracks, crevices, stalls hydroxamate, is formulated and applied as follows: 75 and pens with a knapsack sprayer to run-off.

21 EXAMPLES 107-121 The following compounds are made in the manner of methyl O-(dimethylcarbamyl)thiolacetohydroxamate of 'Example 106 by substituting an equivalent weight of the indicated starting material for the methyl thiolacetohydroxamate of Example 106. The product is formulated and applied in like manner to provide like results.

22 an amount to provide 0.75 lb. of active insecticide per 100 gallons of water. Also added to the same water is a wettable powder formulation of l-(n-butylcarbamoyl)-2- benzimidazolecarboxylic acid, methyl ester, in an amount to furnish 0.75 pound of the active fungicide per 100 gallons. The water containing the compound of Formula 1 and the fungicide is sprayed weekly on field rice at the Starting material Product 107 Methyl thlollsobutyrohydroxamate Methyl O-(dimethylcarbamyl)-thlollsob tym hydroxamate.

108 Methyl p-chlorothlolbenzohydroxamate Methyl O-(dlmethylcarbamyl)-p-chloroth1olbenzohydroxamate.

109 Ethyl thlolacetohydroxamate Ethyl O- dimethylcarbamyl)-th1o1acetohydroxamate.

110 Methyl n-butyrohydroxarnate Methyl O-(dlmethylcarbamyl)-n-butyrohydroxamate.

111 Methyl p-ehlorobenzohydroxamate Methyl O-(dlmethylcarbamyl)-p-chlorobenzohydroxamate.

112 Methyl acetohydroxamate Methyl O-(dlmethylearbamyl)-acetohydroxama e.

113 Benzyl aeetohydroxamate Benzyl O-(dimethylearbamyl)acetohydromma e.

114 Methyl 2-(methylthlo)thlolaeetohydroxamate.. Methyl O-(dlmethylcarbarnyl)-2-(methylthlo) thlolaeetohydroxamate.

115 n-Butyl thlolacetohydroxamate n-Bu yl 0(dln1ethylcarbamyl)-th1o1acetohydroxamate.

116 Methyl p.brornothlolbenzohydroxamate Methyl O-(dlmethylcarbarnyl)-p-bromothlolbenzohydroxamate.

117 Isopropyl thlolacetohydroxamate l opr'opyl 0-(d1methylearbamyl)-thlo1aeet hydroxamate.

118 Isopropyl thlohsobutyrohydroxamate l propyl0-(dlmethylcarbamyl)-thle1lsobutyrohydroxamate.

119 Methyl 3-rnethoxythlolproplonohydroxamate. Methyl O-(d1methylcarbarnyl)-3-methoxythlolpropionohydroxamate.

120 Ethyl thlolproplonohydroxamate E hyl -(dim hylcarbamyl)-thlol ro tenehydroxamate.

121 Benzyl thlolacetohydroxamate Benzyl 0-(dlmethylcarbamyl)-th1o1acet0- hydroxamate.

EXAMPLE 122 rate of 100 gallons per acre providing control of rice Preparation of methyl thlolacetirnidate hydrochloride borers (Chllo P -L and blast a eintermediate EXAMPLE 124 A total of 41 parts of acetonitrile, 250 parts of anhydrous ether and 48 parts of methyl mercaptan are stirred and maintained in an atmosphere of nitrogen as 36.5 parts of dry HCl is gradually added to the mixture. Near the end of the 1101 addition the clear solution becomes cloudy and a precipitate begins to form. The white crystals that form are collected by filtration, rinsed with cold ether, and dried in a vacuum oven at room temperature. A total of 83 parts of hygroscopic, white, crystalline methyl thiolacetimidate hydrochloride is obtained, melting at 81- 89" C.

Other imidate intermediates used in this invention can be made similarly with corresponding alcohols, mercaptans and nitriles.

These imidates are reacted with hydroxylamine hydrochloride in the presence of pyridine to give the corresponding reaction intermediate hydroxamates.

EXAMPLE 123 Percent Methyl O-(methylcarbamyl)thiolacetohydrox amate 97.5 2.5

Synthetic silica The above high-strength composition is prepared by coarse grinding the ingredients and then passing them through a screen having 16 meshes/cm. On adding the concentrate to water at normal use ratio, the active ingredient dissolves.

Thus, the concentrated composition is added to water in Methyl O- (methylcarbamyl -p-chlorothiolbenzohy- This mixture is blended and coarsely micropulverized.

This high-strength composition can be used in this form or further diluted into other useful preparations, which may contain the above compound as the only active ingredient or may contain other pesticides.

The formulation as prepared here is added to water in an amount to provide 0.4 pound of the active compound of this invention per gallons. Also added to this same water is an amount of a commercial Malathion formulation to provide 1.0 pound of Malathion active per 100 gallons. The water containing the two active ingredients is sprayed on tobacco in the field at 10-day intervals controlling tobacco budworms (Heliothis virescens), tobacco hornworms (Manduca sexta), and grasshoppers. The Malathion contributes largely to the control of the grasshoppers. When other insects such as Iune beetles, suckflies or vegetable weevils are present the Malathion can be replaced with TDE, DDT, Guthion," diazinon, parathion or carbaryl.

EXAMPLE 125 Percent Butyl O-(methylcarbamyl)thiolacetohydroxamate 75.0

Sodium alkylnaphthalene sulfonate 2.0 Sodium ligninsulfonate 2.0 Dextrin 4.0 Attapulgite 17.0

The ingredients are blended, coarsely ground through a hammer mill and then passed through a fluid energy mill to produce particles substantially all below 10 microns.

The house fly (Musca domestica), is controlled in barns by using 1 pound of the above formulation in 2.5 gallons of water and spraying the walls, floors, cracks, crevices, stalls and pens with a knapsack sprayer to run-01f. Isopropyl O-(methylcarbarnyl)thioli-sobutyrohydroxamate and ethyl O-(methylcarbamyl)thiolacetohydroxamate can be 23 formulated and applied in like manner, with similar results.

EXAMPLE 126 Percent Isopropyl O (methylcarbamyl)thiolacetohydroxamate 35.0 Ethylene oxide condensate with nonylphenol 4.0 Calcium ligninsulfonate 2.0 Synthetic fine silica 5.0

Kaolinite 54.0

While blending the dry ingredients, the liquid wetting agent is sprayed upon them. The blended composition is then passed through an impact mill and finally reblended.

EXAMPLE 127 Percent Methyl p chloro-O-(methylcarbamyl)thiolbenzohydroxamate 25.00 Calcium ligninsulfonate 6.00 Hydrated attapulgite 2.00 Monobasic potassium phosphate 1.00 Phenylmercury acetate 0.25

Water 65.75

The solid ingredients are blended and micropulverized, mixed with the water and the resulting slurry is sandground in conventional equipment to produce particles substantially all below 2 microns. This formulation is diluted with water and applied to cotton infested with the boll weevil Anthonomus grandis by means of a tractormounted sprayer at the rate of 0.5 to 2 pounds of active ingredient per acre. The infestation is effectively controlled by this application.

EXAMPLE 128 Percent Methyl O-(methylcarbamyl)-p-bromothiolbenzohydroxamate 40.0 Polyoxyethylene sorbitol heptaoleate 8.0 Synthetic fine silica 1.0

Paraflinic hydrocarbon oil 51.0

The slurry is sand-ground to produce particles substantially all below 5 microns. The composition is emulsifiable in water.

This formulation is added to water in an amount to provide 0.25 pound of active ingredient per 100 gallons. The resulting solution-suspension is sprayed on apple trees on a weekly schedule providing control of green peach aphid (Myzus persicae), plum curculio (Conotrachelus neuphar), codling moth (Carpocapsa pomonella), and the red-banded leaf roller (Argyrotaenia velutirzana).

Where more diflicult-to-control insects are present or where spraying intervals are much longer, one or more of the following insecticides is added to the spray in elfective amounts along with the compound of this invention: DDT, methoxychlor, Malathion, parathion, lead arsenate, Guthion," carbaryl or dieldrin.

EXAMPLE 129 Percent Methyl O-(methylcarbamyl)-p-chlorothiolbenzohydroxamate 3.0 Dichlorodifluoromethane 57.0 Trichlorofluoromethane 40.0

The solution is formed under pressure with moderate cooling and packed into pressure vessels.

This aerosol formulation is applied in space application to a restaurant or other type of food establishment. House flies (Musca domestica), present at the time of application are killed.

EXAMPLE 130 Percent n Propyl -O (methylcarbamyl)thiolacetohydroxamate 20.0 Mixed olyoxyethylene sorbitol ester 3.0 Diacetone alcohol 77.0

The ingredients are combined and stirred with warming to produce a homogeneous solution which can be diluted with water. This dilution is made in a manner to provide 1.5 pounds of the active compounds of this invention in 10 gallons of water. An emulsifiable formulation of chlordane is also added in an amount to provide 1 pound active in 10 gallons. The resulting composition is then sprayed on surgarcane seed pieces in the open furrow at the time of planting at the rate of 10 gallons per 10,000 feet of row providing control of a variety of insects.

EXAMPLE 13 1 Percent M e t h y l O (methylcarbamyl(thiolbutyrohydroxmate 20.0 Methylene chloride 74.0

Blend of oil-soluble sulfonates and polyoxyethylene ethers 6.0

The ingredients are combined and stirred to produce a homogeneous emulsifiable solution. This emulsifiable formulation is added to water in an amount to provide 5 pounds of active ingredient per gallons. Sprayed by air on field sugarcane foliage at the rate of 20 gallons (1.0 pound active) per acre, at Weekly intervals, this preparation provides control of armyworms and the sugarcane borer (Dz'atraea saccharalis). Where spray intervals are significantly longer than one week, one or more of the following insecticides is added to the spray in an effective amount: Toxaphene, carbaryl, endrin or Guthion.

EXAMPLE 1 3 2 Percent M e t h y l O (methylcarbamyl)thiolacetohydroxamate 5 .0 Trimethylnonyl polyethylene glycol ether 2.0 Phenylmercury acetate 0.1 Water 92.9

The ingredients are stirred to produce a solution.

This composition is diluted with water to a final concentration of 0.1% active. House flies (Musca domestica), and certain other flies such as stable flies (Stomoxys calcitrans), are controlled in farm buildings, in barnyards and other outdoor locations by spraying this formulation as a space spray by mist blower or directly to the flying 0r resting insects by use of a hydraulic sprayer.

The formulation above, diluted to 10 pounds active ingredient per 100 gallons is also applied at a rate of 100 gallons per acre to land being renovated for pasture, in order to control ticks.

EXAMPLE 133 Percent Methyl O-(methylcarbamyl)thiolacetohydroxamate 36.1 Dimethylformamide 63.9

The above water-soluble concentrate which contains 3 pounds active per gallon is prepared by blending the components in a stirred vessel until solution of the active compound is complete. This preparation is sprayed by air as an ultra low volume (ULV) application on areas of deciduous forest at the rate of 0.30.5 gallon per acre providing control of the gypsy moth (Porthetria dispar). Where more resistant insects are also present, one or more of the following insecticides are added in effective amounts to the spray containing the compound of this invention: methoxychlor, DDT, carb'aryl, Malathion or Toxaphene.

The above formulation is sprayed by air, without dilution, at the rate of 0.33 gallon per acre over forest areas containing fir, spruce, larch, hemlock and pine trees, for the control of the spruce budworm, (Choristoneura fumiferma). The areas are sprayed when the larvae are in the fourth and fifth instars. Nozzles and spray pressure are adjusted such that most of the droplets are approximately 5 microns in diameter. Excellent control of the budworm is obtained which results in good, sturdy shoot growth and a dark green, thrifty appearance. The tops of trees in ad jacent unsprayed areas appear as though scorched by fire, and many of those trees heavily infested die.

In another area, a forest consisting primarily of balsam fir is sprayed with a solution prepared by diluting one gallon of the above formulation with 48 gallons of water. Application at the sub-lethal rate of one gallon of the dilute solution per acre is sufficient to knock the spruce bud-worm larvae out of the trees and onto the ground below. Being unable to return to the trees, the larvae no longer impede the normal growth of the trees.

The above formulation is added to water in an amount to provide 0.75 pound of active ingredient per 100 gallons. The water containing the insecticide is then sprayed on field rice at .10-day intervals providing control of rice borers, Chilo spp.

Where insects such as the grape colaspis and stink bugs are present in addition to rice borers, other insecticides such as EPN, carbaryl, Guthion, Malathion, methyl parathion or parathion are also added to the spray.

EXAMPLE 134 Percent Methyl O-(methylcarbamyl)acetohydroxamate 45 Trimethylnonyl polyethylene glycol ether Cyclohexanone 50 The ingredients are combined and stirred to produce a homogeneous solution which can be diluted with water and applied as an aqueous solution.

A finished spray containing 1% of this formulation applied to run-off by means of a knapsack sprayer effectively controls green peach aphids (Myzus persicae), infesting oarnations.

EXAMPLE 135 Percent Methyl O-(met-hylcarbamyl)-butyrohydroxamate 20 Xylene 74 Blend of oil-soluble sulfonates and polyoxyethylene ethers The ingredients are combined and stirred to produce a homogeneous solution. This formulation is emulsified with water and applied in the manner described for the formulation of Example 131.

EXAMPLE 136 Percent Methyl p chloro O (methylcarbamyl)benzohydroxamate 75 Sodium alkylnaphthalenesulfonate 2 Calcium ligninsulfonate 2 Kaolinite clay 21 The ingredients are thoroughly blended and micropulverized to produce particles substantially all below 50 microns. The composition may be used as a dust base or as a Wettable powder.

EXAMPLE 137 Percent Methyl O-( methylcarbamyl)thioacetohydroxamate 5.0 Granular attapulgite (0.6-1.4 mm.) 95.0

The active component is warmed to 75 C. with three parts of water per part of active and the resulting warm solution is sprayed on the granules which are tumbled in a mixer. The granules are dried in a circulating air oven and then are ready for application.

The granules prepared as described above are applied to the soil during the planting of corn, in the furrow, at a rate to provide 2.0 pounds of active ingredient per acre of field. This treatment gives control of corn rootworms and other soil insects. Where more difficult-to-kill soil insect species are also present, granules containnig one or more of the following insecticides are added in effective amounts: parathion, aldrin, diazinon or phorate.

EXAMPLE 1 3 8 Percent Methyl O-(methylcarbamyl)thioacetohydroxamate 10.0 Granular attapulgite (0.40-0.85 mm.) 90.0

The active ingredient is dissolved in a minimum amount of methylene chloride and is then sprayed upon the attapulgite in a blender. The methylene chloride is removed by air drying.

The granules prepared as described above are applied in the planting furrows of potatoes at the rate of two pounds of active ingredient per 10,000 linear feet of row. This treatment controls white-fringed beetle grubs (Graphognathus leucoloma), in the soil and potato aphids (Macrosiphum euphorbiae), on the foliage for an extended period. This foliage protection is due to the systemic movement of the compound of this invention from the soil up into the foliage. Where more diflicult-to-kill insect species are also present in the soil, granules containing one or more of the following insecticides are added in effective amounts: chlordane, DDT, diazinon or parathion.

EXAMPLE 139 Percent Methyl O(methcarbamyl)thioacetohydroxamate 5.0 Granular attapulgite (0.61.4 mm.) 95.0

The finely divided active component is tumbled with the granules in order to coat the surface. The entire mass is heated to C. to melt the active compound which is absorbed in and on the surface of the granules. The cooled granules are then ready for application.

The granules prepared as described above are applied to small sweet corn plants at the rate of 20 pounds per acre. The application is made in such a way that the granules roll down into the whorls of the plants. Corn earworms (Heliothz's zea), attacking the growing area are controlled.

EXAMPLE 140 Percent Methyl 0 (methylcarbamyl)-p-chlorothio-benzohydroxamate 20.0 Sodium sulfate 10.0 Calcium ligninsulfonates 13.0 Mississippi sub-bentonite 31.0 Kaolinite 26.0

This mixture is coarsely micropulverized and blended with about 18% by weight of Water. This moist composition is extruded and cut to form pellets which are dried prior to use.

The pellets described here are used in the same manner as the granules of Example 139 except that the use rate is 5 pounds of pellets per acre. The insecticidal results of this application are the same as those obtained with the granules.

EXAMPLE 141 EXAMPLE 142 Percent Methyl O-methylcarbamyl)thiolacetohydroxamate- 1:1 complexe with urea 95.0 Synthetic silica 5.0

The above composition is prepared by micropulverizing the ingredients to a particle size passing a 16 mesh/ cm. screen.

The 1:1 complex of methyl O-carbamylthiolacetohydroxamate with urea can be formulated in like manner.

The formulation of methyl carbamylthiolacetohydroxamate described above is added to water in an amount to provide 6 pounds of 1:1 complex per 100 gallons of water. This is sprayed on cotton plants at the rate of 25 gallons (1.5 pounds of complex) per acre providing control of boll weevil (Anthonomus grandz's), and bolloworms (Heliothis zea). Where more difficult-to-kill insect species are also present, an insecticdal amount of one or more of the following materials is added to the spray: DDT, endrin, carbaryl, Malathion, methyl parathion, parathion, Guthion, or Toxaphene.

EXAMPLE 143 Percent 1,4 dichloro-2,S-dimethoxybenzene 50.0

Mehtyl O-(methylcarbamyl) thiolacetohydroxamate 25.0 Octoylphenyl polyethylene glycol ether 1.0 Sodium alkylnaphthalenesulfonate 0.7 Sodium lignin sulfonate 2.75 Synthetic silica 0.75 Diatomaceous earth 2.75

Thiram 10.0 Magnesium carbonate 7.0

The above components are blended and micopulverized to pass a 24 mesh/cm. screen. This wettable powder can be applied to spraying or in a seed treater to coat seeds.

The above formulation is applied to cotton seed in a standard seed treater at the rate of 12 ounces of formulation per 100 pounds of cotton seed along with 3 ounces of Ceresan L per 100 pounds of seed. Such treatment prevents seed and seedling loss due to Pythium and Rhizoctonia as well as seedling damage by aphids and certain other insects. Where other soil fungi such as Fusarium are considered to be a hazard, 1-(n-butylcarbamoyl)-2 benzimidazolecarbamic acid, methyl ester, is also added to the seed at the same rate as the 1,4-dichloro-2,5-dimethoxybenzene.

EXAMPLE 144 Percent Methyl O- methylcarbamyl) thiolacetohydroxamate 50.0 Ethylmercury p-toluenesulfonanilide 2.0 Thiram 25.0 Synthetic silica 3.0 Attapulgite clay 16.5 Sodium alkylnaphthalene sulfonate 1.0 Calcium lignin sulfonate 2.5

The above formulation is added to cotton seed in a to a particle size essentially below 50 microns. This wettable powder can be suspended in water and used to treat seeds or with appropriate dilution, as a spray.

The above formulation is adde to cotton seed in a standard slurry seed treater at the rate of 16 ounces of formulation per 100 pounds of seed. This treatment protects the seed from attack by soil fungi, and insects. It also protects the seedling from attack by cotton aphids (Aphis gossypii), for an extended period by systemic movemerit of the methyl 0 (methylcarbamyl)thiolacetohydroxamate from the area of the seed up into the seedling.

EXAMPLE 145 Percent 28 EXAMPLE 145-Continued Percent Attapulgite clay 51.5 Sodium alkylnaphthalene sulfonate 1.0 Calcium lignin sulfonate 2.5

The above components are blended and micropulverized to a particle size essentially below 50 microns. This wettable powder can be suspended in water and used to treat seeds or, with approriate dilution, as a spray.

The formulation above is added to cotton seed in a standard slurry seed treater at the rate of 10 ounces of formulation per pounds of seed. This treatment protects the seed from attack by soil fungi, and insects, and results in a fine stand of cotton seedlings.

EXAMPLE 146 Percent Methyl O- (methylcarbamyl) thiolacetohydroxamate 50.0 Ethylmercury p-toluenesulfonanilide 0.1 Thiram 25.0 Synthetic silica 3.0 Attapulgite clay 18.4 Sodium alkylnaphthalene sulfonate 1.0 Calcium lignin sulfonate 2.5

The above components are blended and micropulverized to a particle size essentially below 50 microns. This wettable powder can be suspended in water and used to treat seeds or, with appropriate dilution, as a spray.

The above formulation is added to cotton seed in a standard slurry seed treater at the rate of 15 ounces of formulation per 100 pounds of seed. This treatment protects the seed from attack by soil fungi and insects. It also protects the seedling from attack by cotton aphids (Aphis gossypii), for an extended period by systemic movement of the methyl O-(methylcarbamyl)thiolacetohydroxamate from the area of the seed up into the seedling.

EXAMPLE 147 Percent Methyl O-(methylcarbamyl) thiolacetohydroxamate) 50.0 1- (n-butylcarb amoyl) -2-benzimidazolcarboxylic acid, methyl ester 25.0 Kaolinite clay 20.0 Sodium dihydrogen phosphate 1.0 Sodium alkylnaphthalene sulfonate 2.0 Calcium lignin sulfonate 2.0

The above components are blended and micropulverized to a particle size essentially below 25 microns. This wettable powder is suitable for use in spraying fruit trees and vegetable crops.

This formulation is added to water at the rate of 1.0 pound of formulation per 100 gallons of water. When the resulting preparation is sprayed on apple trees on a regular schedule at the rate of 300 gallons per acre, the trees are protected from attack by insects such as aphids, codling moth (Carpocapsa pomonella), and plum curoulio (Conotrachelus nenuphar), as well as from diseases including apple scab and powdery mildew.

The following formulation is prepared in the manner described above, and when used in a similar manner, gives similar results.

Percent Methyl O-(methylcarbamyl)thiolacteohydroxamate 50 tit-(2,4-dlChlOIOPh6l'lYl)-0L-Ph6ny1 5 pyrimidinemethanol 4 Kaolinite clay 41 Sodium dihydrogen phosphate 1 Sodium alkylnaphthalene sulfonate 2 Calcium lignin sulfonate 2 29 EXAMPLE 148 Percent Methyl O (methylcarbamyl)thiolacetohydroxamate 40.0 Streptomycin sulfate 1.0 Maneb 40.0 Methylated cellulose 2.0 Sodium alkylnaphthalenesulfonate 1.0 Kaolinite 16.0

The above ingredients are blended and micronized to a particle size passing a screen having 0.25 millimeter square openings. This wettable powder when suspended in water is suitable for spraying vegetable crops.

The formulation described above is added to water at the rate of 3.0 pounds per 100 gallons. When this liquid is sprayed on tomato plants on a weekly schedule, the plants are protected from attack by insects and such dis eases as bacterial spot and late blight.

Percent 1,4-dichloro-2,5-dimethoxybenzene 20.0 Methyl O (methylcarbamyl)thiolacetohydroxyamate 10.0 Trimethylnonyl polyethylene glycol ether 5.0 Methylene chloride 65.0

The above emulsifiable composition is prepared by blending the ingredients until a homogeneous solution is obtained. This formulation can be used as such or it can be used to prepare a granular composition by spraying on preformed granules (size 0.6-1.4 mm.) followed by drying to remove the methylene chloride. The granules are applied in the furrow at a rate of 3 pounds total active ingredients per 10,000 linear feet of row while planting beans. This gives good control of soil fungi, particularly Rhizoctonia spp., and protects the seedling bean plants from aphids.

lEXAMPLE 150' Percent Methyl O (methylcarbamyl)thiolaceto h y d r o xamate 20.0 Methylmercury 2,3-dihydroxpropyl mercaptide 0.5 Methylmercury acetate 0.1 Methanol 50.0 Water 29.4

The above solution is prepared by mixing the components. It can be used directly for seed treatment and also can be diluted with water and sprayed. When this formulation is applied to cotton seed at the rate of 30 ounces per 100 pounds, the seed is protected from fungus decay in the soil and the seedlings that develop resist attack by aphids and other insects due to the systemic movement of the compound of this invention.

EXAMPLE 151 Percent Methyl O (methylcarbamyl)thiolacetohy dr oxamate 23.0

EPN 23.0

Dimethylformamide 49.0 Blend of polyoxyethylene ethers of oil-soluble sulfonates The above components are mixed to form a homogeneous solution which can be applied directly, as in ULV application, or which forms a sprayable suspension when added to water, Xylene, or non-phytotoxic spray oils. Methyl O-carbamylthiolacetohydroxamate can be formulated and applied in like manner. The above formulation is added to water at the rate of 2.0 pounds per 100 gallons. When the resulting suspension is sprayed on potato plants at the rate of 100 gallons per acre on a regular weekly schedule, the plants are protected from attack by a wide variety of insects.

EXAMPLE 1 5 2 Percent Methyl O-carbamylthiolacetohydroxamate 15.0 DDT 30.0 Dimethylformamide 50.0

Blend of polyoxyethylene ethers of oil-soluble sulfonates 5 .0

EXAMPLE 153 Percent Methyl O-carbamylthiolacetohydroxamate 10.0 Toxaphene 40.0 Dimethylformamide 45.0 Blend of polyoxyethylene ethers of oil-soluble sulfonates 5.0

The above components are mixed and warmed to form a homogeneous solution which can be sprayed as a ULV application or which forms a sprayable suspension when added to water, non-phytotoxic spray oils, or low-boiling aromatic hydrocarbons.

Strobane can be substituted for toxaphene and dimethylacetamide for dimethylformamide with similar results. These formulations are useful in protecting a wide variety of plants from a number of damaging insects.

EXAMPLE 154 Formulations of both methyl O-(methylcarbamyl) thiolacetohydroxamate and methyl O-carbamylthiolacetohydroxamate are prepared as described in Example 123. Two pounds of each formulation is added to a gallon tank of water. This dilution is then sprayed on cotton plants at the rate of 25 gallons per acre (providing about 0.12 pound of each of the two active compounds of this invention). Excellent control of a wide variety of insect pests is obtained.

EXAMPLE 155 Percent Methyl O-carbamylthiolacetohydroxamate 95.0 5.0

Synthetic silica The above high-strength composition is prepared by coarse grinding and screening through a screen having 0.42 milimeter square openings.

This composition is stirred into water in an amount to provide 0.5 pound of the active ingredient per 100 gallons. The resulting solution is applied as a wetting spray to cabbage plants on which cabbage loopers (T richoplusia ni), are feeding. Good control of the cabbage loopers is obtained.

EXAMPLE 156 Methyl O-(methylcarbamyl) -p-nitrothiolbenzohydroxamate is incorporated in a synthetic laboratory die for boll weevils at a rate of 0.0002 percent by weight (2 parts per million). Weevils feeding on this diet lay eggs but none of these eggs hatch. Similar weevils feeding on the same diet without the methyl O-(methylcarbamyD-pnitrothiolbenzohydroxamate lay eggs that hatch to produce normal living young.

31 EXAMPLE 157 Percent 1,2-dibromo-3-chloropropane 60 Methyl O-(methylcarbamyl)thiolacetohydroxamate 12 Blend of alkylarylpolyether alcohols with organic sulfonates 8 Alkylnaphthalenes (principally c methylnaphthalene) 20 These ingredients are combined with simple mixing to form a homogeneous liquid.

This emulsifiable liquid is dispersed in water at a rate that provides 36 pounds of the active ingredients per 100 gallons of water. The resulting dilute emulsion is sprayed over the root zone of rose bushes at a rate of 100 gallons per acre. The area is then irrigated with a quantity of water sufficient to carry the active ingredient into the root zone of the rose bushes. Excellent control is obtained of dagger nematodes (Xiphinema spp.), allowing the treated bushes to grow in a normal manner. In addition, the bushes are protected from aphids and other insects. Similarly, infested rose bushes which are not treated grow poorly and produce flowers having little ornamental value.

EXAMPLE 158 Percent Methyl O (methylcarbamyl)thiolacetohydroxamate 26.0

o-Cresol 17.4

Xylene 52.0 Sodium dodecylbenzene sulfonate 4.6

The above ingredients are stirred with warming until a homogeneous solution is obtained. The resulting emulsifiable concentrate is added to Water in an amount to give 65 grams of active ingredients per 100 liters of spray. This emulsion is sprayed on apple trees to the point of run-off by means of a high pressure hydraulic sprayer. Sprays on a weekly schedule provide control of green apple aphid (Aphis pomi), codling moth (Carpocapsa pomonella), plum curculio (Conotrachelus nenuphar), and red-banded leaf roller (Argyrotaenia velutinana). One or more of the following insecticides in elfective amounts can be added to the spray when a longer interval between applications is desired or it is needed to control other especially diflicult-to-control pests: methoxychlor, Malathion or carbaryl.

EXAMPLE 1 5 9 Percent Powder of Example 2 21.5 Activated charcoal 78.5

Percent Methyl O (methylcarbamyl)thiolacetohydroxamate 38.0 5,6 dihydro-2-methyl-p-oxathiin-3-carboxanilide 37.0

Octyl phenyl polyethylene glycol ether 1.0 Sodium alkyl naphthalene sulfonate 0.75 Sodium lignin sulfonate 2.75 Synthetic silica 0.75 Diatomaceous earth 2.75 Thiuram 10.0 Magnesium carbonate --'=a;i a:;aa:=.==- 7.0

The above components are blended and micropulverized to pass a 24 mesh/cm. screen. The resulting wettable powder can be applied by spraying or in a seed treater to coat seeds.

The above formulation is applied to wheat seed in a standard seed treater at the rate of 12 ounces of formulation per 100 pounds of wheat along with 1 ounce of Ceresan L. When plated the treated seed germinates and grows well protected from damage by the greenbug (Schizaphis graminum), as well as from fungi including loose and covered smut.

EXAMPLE 16 1 Percent Bran 98 Methyl O-(methylcarbamyl)thiolacetohydroxamate 2 The bran is tumbled while a 20% acetone solution of methyl O-(methylcarbamyl)thiolacetohydroxamate is sprayed over the surface. After thorough mixing the contents of the tumbler are discharged into a shallow pan and air dried.

Just prior to use the bait is moistened with one-half its weight of water and then broadcast over an area planted to truck crops with a spreader at the rate of 2 kg./ha. It is spread evenly over both the foliage and soil, and gives excellent control of garden slugs. The bait is reapplied on an as-needed basis to control this pest. As a beneficial side effect, the bait also controls grasshoppers, cutworms, armyworms, crickets and earwigs.

The dry bait described above is moistened with half its weight of water containing 2% black strap molasses. It is spread evenly in a band over tobacco plants at the rate of 1 kg. per 8,900 meters of row on a 7-day schedule starting at the first signs of serious pest infestation. Good control of both the tobacco budworm and hornworm is obtained.

EXAMPLE 162 Dry dog food meal 99 Methyl O (methylcarbamyl)thiolacetomethoxamate The dry dog food meal is tumbled while a 20% solution of the active ingredient dissolved in acetone is sprayed over the surface. After thorough mixing, the bait is poured into shallow pans and air dried. It may be packaged for use as such. Alternatively, suflicicnt water is added to plasticize the mass and it is extruded through a 3 cm. die, chopped into sections and dried. These pellets are placed singly into especially made cans which have holes cut along the bottom edge to allow the insects to feed. Cans are placed out of reach of children and pets in areas in fested with cockroaches. Excellent control of these pests is obtained.

Combinations of methyl O-(methylcarbamyl)thiolacetohydroxamate with S-methyl 1-(dimethylcarbamoyl)-N- (methylcarbamoyl)oxy]thioformimidate are especially useful for controlling both insects and nematodes. The combinations can be used in the ratios of 1:10 to 10:1 with 1:3 to 3:1 being preferred. They can be made either prior to formulation or after each has been formulated separately. The combinations can be formulated in as many different ways as are described for the separate active ingredients. Use rates vary with the crop being protected, weather conditions, and the specific pests controlled, but generally are from 2 to 12 pounds per acre when used in the furrow at planting time, and from /2 to 1 /2 pounds per 100 gallons per acre when used as a foliar spray.

EXAMPLE 163 Percent Methyl O-(methylcarbamyl)thioacetohydroxamate 5 S-methyl l-(dimethylcarbamoyl) N [(methylcarbamoyl)oxy1thioformimidate 5 Dimethylformamide 1O M.P.78 Celatom granules aaaaaa a- The two active ingredients and the dimethylformamide are stirred into solution, and then sprayed over the Celatom granules which are being tumbled in a rotary blendor. Care is taken to assure good distribution of the active ingredients onto the granules. The granule absorbs the dimethylformamide making it unnecessary to dry them. They are then packaged for use.

The above formulation is applied at the rate of 6 pounds active per acre in a 18-inch band to a field of tobacco just prior to transplanting time. The band is rotovated lightly to a depth of 4 inches and the young tobacco plants are set out. The field is known to be infested with several species of nematodes such as Melio dogne incognita, Tylenchorhynchus spp., Pratylenchus spp., Paratylenchus spp., and Xiphinema spp. The tobacco plants treated in this fashion are observed to grow Well free from the depredations of both the nematodes, and early season insects such as flea beetles. Conventional insecticide sprays may be applied late in the season for additional control of tobacco budworm and/or hornworm, if desired.

EXAMPLE 164 One hundred parts of the dimethylformamide solution of Example 163 is diluted further with 100 parts of dimethylformamide to provide a liquid formulation containing 2 pounds of active ingredient per gallon.

Three pints of this formulation (commodity basis) are diluted with 100 gallons of water and used to spray an acre of tobacco plants. These plants are sprayed in a similar fashion from shortly after transplanting to two weeks before harvest on a 6-7 day schedule. Excellent control of the following insects is obtained: flea beetles, hornworms, budworms and cabbage loopers. In addition, the plants are larger and more 'vigorous than similar but untreated plants because of the nematode control which is provided by this combination.

EXAMPLE 1 65 Percent Methyl O-(methylcarbamyl)thioacetohydroxamate 18 S-methyl l-(dimethylcarbamoyl) N [(methylcarbamoyl)oxyJthioformimidate 18 Dimethylformamide 75 The above-listed ingredients are stirred together to form a solution with a total active ingredient content of 2 pounds per gallon.

One quart of this solution is extended with 100 gallons of water and sprayed over an acre of potatoes repeatedly on a 5-7 day schedule throughout the growing season. Excellent control of such insects as flea beetles, Colorado potato beetle, potato tuber worm and aphids is observed resulting in a higher yield of potato tubers than obtained from an adjacent but untreated acre plot. The tubers are also higher in quality due to the much lower incidence of attack by the root knot nematode, Meliodogyne incognito.

I claim:

1. A composition useful as an insecticide comprising an agricultural adjuvant and an insecticidal amount of a compound of the formula wherein R is alkyl of 1 through carbon atoms, haloalkyl of 1 through 5 carbon atoms containing 1 to 5 chlorine atoms, 1 to 5 bromine atoms or 1 to 11 fluorine atoms; alkoxyalkyl of 2 through 5 carbon atoms, alkylthio alkyl of 2 through 5 carbon atoms or cycloalkyl of 3 through 5 carbon atoms;

R is hydrogen or methyl;

R is hydrogen or methyl;

R is alkyl of 1 through 6 carbon atoms; and

Q is sulfur.

2. A composition of claim 1 in which the compound is methyl O-(methylcarbamyl)thiolacetohydroxamine.

3. A composition of claim 1 in which the compound is methyl 0- (methylcarbamyl thiolisobutyrohydroxmate.

4. A composition of claim 1 in which the compound is methyl O-carbamylthiolacetohydroxamate.

5. A composition of claim 1 in which the compound is methyl O-(methyloarbamyl)thiolpropionohydroxamate.

6. A composition of claim 1 in which the compound is ethyl O- (methylcarb amyl thiolacetohydroxamate.

7. A composition of claim 1 in which the compound is ethyl O-carbamylthiolacetohydroxamate.

8. A composition of claim 1 in which the compound is methyl O-carbamylthiolpropionohydroxamate.

9. A composition of claim 1 in which the compound is ethyl O-oarbamylthiolpropionohydroxamate.

10. A composition of claim 1 in Which the compound is ethyl O- (methylcarbamyl thiopropionohydroxarnate.

11. A composition useful as an insecticide comprising an agricultural adjuvant and an insecticidal amount of -a compound of the formula R is alkyl of 1 through 3 carbon atoms, and R is alkyl of 1 through 3 carbon atoms.

12. A method for controlling insects comprising apply- 1ng to a locus to be protected an insect-controlling amount of a compound of the formula wherein R is alkyl of 1 through 5 carbon atoms, haloalkyl of 1 through 5 carbon atoms containing 1 to 5 chlorine atoms, 1 to 5 bromine atoms or 1 to 11 fluorine atoms; alkoxyalkyl of 2 through 5 carbon atoms, alkylthioalkyl of 2 through 5 carbon atoms or cycloalkyl of 3 through 5 carbon atoms;

R is hydrogen or methyl;

R is hydrogen or methyl;

R is alkyl of 1 through 6 carbon atoms; and

Q is sulfur.

13. A method according to claim 12 wherein the compound is methyl 0 (methylcarbamyl)thiolacetohydroxamate.

14. A method according to claim 12 wherein the compourtid is methyl 0 (methylcarbamyl)thiolacetohydroxama e.

15. A method for controlling insects comprising applying to a locus to be protected an insert-controlling amount of a compound of the formula wherein R is hydrogen or methyl, R is alkyl of 1 through 3 carbon atoms, and R is alkyl of 1 through 3 carbon atoms.

16. A method according to claim 15 wherein the compound is methyl O-carbamylthiolacetohydroxamate.

17. A method according to claim 15 wherein the compound is methyl O-(methylcarbamyl)thiolacetohydroxamate.

35 18. A method for controlling insects comprising applying to the plants an insert-controlling amount of a compound of the formula wherein 19. A method according to claim 18 wherein the compound is methyl O-(methylcarbamyl)thiolacetohydroxamate.

20. A method according to claim 18 wherein the compound is methyl O-carbamylthiolacetohydroxamate.

21. A method for controlling insects comprising apply- 36 ing to the plants an insect-controlling amount of a compound of the formula wherein R is hydrogen or methyl, R is alkyl of 1 through 3 carbon atoms, and R is alkyl of through 3 carbon atoms.

22. A method according to claim 21 wherein the compound is methyl O-carbamylthiolacetohydroxamate,

23. A method according to claim 21 wherein the compound is methyl O-carbamylthiolacetohydroxamate,

References Cited UNITED STATES PATENTS 2,786,865 3/1957 Copenhaver 260566 A 3,217,036 11/1965 Payne 260566 A 3,217,037 11/1965 Payne et a1 260566 A 3,063,823 11/1962 Kiible et a1 71-2.6

3,223,733 12/1965 Heiss et a1 260566 OTHER REFERENCES Metcalf, Organic Insecticides, pp. 317-329 (1955).

JEROME D. GOLDBERG, Primary Examiner 

